Copolymerization of conjugated diolefins with mono-olefin hydrocarbon material in the presence of vanadyl chloride



United States Patent C) 3,345,349 COPOLYMERIZATION F CONJUGATED DIOLE- FINS WITH MONO-OLEFIN HYDROCARBON MATERIAL IN THE PRESENCE OF VANADYL CHLORIDE Noboru Yamada, Keizo Shimada, and Hiroshi Ichida, Yamaguchi-ken, Japan, assignors to Teijin Limited, Nishi-ku, Osaka, Japan, a corporation of Japan No Drawing. Filed Apr. 26, 1963, Ser. No. 276,097 Claims priority, application Japan, Apr. 30, 1962, 37/17,783; Apr. 2, 1963, 38/16,880 6 Claims. (Cl. 260-853) This invention relates to a method of copolymerizing conjugated diolefins with monoolefin hydrocarbons.

Heretofore, oily or rubber-like polymers have been manufactured from monoolefin hydrocarbons such as propylene and isobutylene by polymerizing the same in the presence of a so-called Friedel-Crafts type catalyst such as anhydrous aluminum chloride.

The method of this invention is that for copolymerizing monoolefin hydrocarbons with conjugated diolefins wherein vanadyl chloride (VOCl is used as the catalyst.

Vanadyl chloride exhibits catalytic activity markedly different from that of the so-called Friedel-Crafts type catalyst such as anhydrous aluminum chloride. Namely, while anhydrous aluminum chloride, as is known, is used as a catalyst in the polymerization of isobutylene, vanadyl chloride shows practically no catalytic activity in the polymerization of isobutylene. Again, according to our research, it is found that vanadyl chloride has a very high catalytic activity in polymerization of conjugated diolefins such as isoprene or butadiene, and quickly polymerizes the same even under low temperatures. In contrast to this, anhydrous aluminum chloride and other Friedel-Crafts type catalysts show remarkably less activity in polymerization of conjugated diolefins. According to the method of this invention, by using vanadyl chloride (VOCl as the catalyst, monoolefin hydrocarbons can be quickly copolymerized with conjugated diolefins such as isoprene and butadiene in a good yield. Particularly, this invention is based on the discovery of the fact that such a monomer which is by itself hardly polymerizable by vanadyl chloride catalyst as isobutylene can be polymerized upon addition of a minor amount of conjugated diolefin. The copolymers obtained by the present method have wide and valuable utilities as synthetic resins, elastomer, or adhesive agent, etc.

While vanadyl chlorides includes a number of compounds such as those represented generally by the formulae VOCl VOCI V001 and V O Cl, among these, the vanadyl chloride having the formula VOCl is used particularly as the catalyst in this invention. Hence, vanadyl chloride, as used herein, refers to the vanadyl chloride having the formula VOCl unless indicated otherwise.

While all the compounds represented by the formulae VOCI V001 and V O Cl are solid at room temperature, the vanadyl chloride (VOCl used as the catalyst in this invention is liquid (boiling point 126-127 C.) at room temperature. This vanadyl chloride may be obtained, for example, by mixing vanadium trioxide (V 0 and carbon, heating the mixture to about 400 C. while passing through dry chlorine gas, and thereafter distilling and purifying the resulting reaction product. It may also be possible to prepare said vanadyl chloride from phosphorus pentoxide and vanadium pentoxide. However, the process by which vanadyl chloride is prepared is of course not critical, it being possible to use according to this invention, as the catalyst therefor, vanadyl chloride produced by any process.

3,345,349 Patented Oct. 3, 1967 The vanadyl chloride used in the method of this invention which is a yellow liquid having boiling point of 126.-127 C., as described above, is characterized in that it reacts with water or alcohol and decomposes. v

The conjugated diolefins useful for the copolymerization of the present invention include, for example, butadiene 1,3, isoprene (2 methylbutadiene 1,3), 2,3 dimethylbutadiene-l,3, 2,3-dimethylpentadiene-1,3, 2,4-dimethylpentadiene 1,3, 2,3,4 trimethylheptadiene-LS, 2- ethylbutadiene 1,3, 2-phenylbutadiene-l,3, 2,3-dipheny1- butadiene 1,3, 2 methylpentadiene-L3, 2 methylhexadiene-l,3, 2,5-dimethylhexadiene-2,4, 7-methyl-3-methylene-l, 6-octadiene and other polymerizable methyl-, ethyl-, isopropyl-substituted butadienes, pentadienes, hexadienes, and heptadienes.

The monoolefin hydrocarbons copolymerizable with the conjugated diolefins according to the invention include, for example, propylene, n-butene-l, isobutylene, pentene-l, isopentene, hexene-l, isohexene, and other methyl-, ethyl-, propyl-, isopropyl-substituted a-olefins of 4-10 carbons, and certain 2-olefins such as butene-Z, 2- methylbutene-2. Again the monoolefin hydrocarbons include aryl-substituted monoolefin hydrocarbons such as styrene, vinyltoluenes, a-methylstyrenes, and vinyl naphthalenes. Mixtures of two or more of the foregoing are also usable.

The copolymerization of conjugated diolefins with monoolefin hydrocarbons according to the invention is practiced under optional presence of an inert organic solvent, the presence of an inert organic solvent however being preferred. As such inert organic solvent, saturated hydrocarbons such as hexane, heptane, octane, or halogenated hydrocarbons such as methylene chloride, ethylene chloride, chloroform, carbon tetrachloride are suitable, and those which do not contain compounds having active hydrogen such as water and alcohol are used.

The method of this invention may be practiced as follows:

To the mixture of one or more of conjugated diolefins (for example, isoprene) with one or more of monoolefin hydrocarbons such as isobutylene, vanadyl chloride is added in the absence of oxygen and water, and in the optional presence of an inert solvent, mixed at temperatures ranging from -l00 to C., preferably 70 to 50 C. and reacted. The pressure condition may be any of the state, reduced, normal, or elevated. The polymerization progresses rapidly. After completion of the reaction, alcohol is added to the polymeric mixture to stop the reaction. By the addition of alcohol, the catalyst decomposes, and the reactant liquid mixture turns brown from green or yellow color, and white or somewhat colored polymer precipitates. The precipitated polymer is separated, dissolved in n-heptane, benzene, etc., and -re-precipitated by addition thereto of alcohol. After separation, the; re-precipitated polymer is further washed thoroughly with alcohol, thereby to be removed of catalyst residues and refined. The alcohol to be used in these operations may be any of methyl, ethyl, or isopropyl alcohols. Thus obtained polymer is amorphous rubber-like substance or SOlld, sometimes containing insoluble, white powdery portions insoluble in heptane or benzene.

The amount of vanadyl chloride used is 01-10% by Weight, preferably 0.55% by weight, based on the total of the weight of the conjugated diolefin, monoolefin hydrocarbon and the inert organic solvent. The inert organic solvent, on the other hand, is generally used in an amount preferably from 0.5 to 10 times by weight of the conjugated diolefin and monoolefin. The amount of conjugated diolefin is within 0.001-10 by weight ratio to monoolefin hydrocarbon, preferably within the range of 0.01-0.5.

For a still clearer understanding of the invention, the following examples are given.

Example 1 Ten millimols of vanadyl chloride were filled in an ampoule in dry nitrogen current. Said ampoule was them packed in a 100 cc. pressure bottle together with 50 cc. of refined n-heptane and 0.0504 mol (3.43 g.) of refined isoprene. The bottle was then cooled in a Dry Iceacetone bath of 70 C., removed of air, and was added with 0.163 mol (9.41 g.) of refined isobutylene (isobutylene/isoprene: 3 .24 mol ratio) The reaction vessel was then taken out of the cooling bath. When the vessel as a whole reached the reaction 50 cc. of refined n-heptane, 0.0504 mol (5 cc. at C.) of refined isoprene and 0.131 mol (15.0 cc. at 20 C.) of styrene. Air was removed from the bottle. When the reaction vessel as a whole reached the reaction temperature of 0 C., the ampoule was broken to start the polymerization. After 18 hours of polymerization, entirely solidified reaction mixture was poured into '50 cc. of cold methanol. And the polymer was pulverized, and subjected to several further washings with methanol, thereby 12.8 g. of white polymer powder were obtained. The yield Was 75.8%.

Example 13 All the operations are same to the above Example 11,

temperature of 0 C., the ampoule of vanadyl chloride 15 except changing the kinds of the solvents used.

Monomer Reaction Conditions vanadyl Solvent (00.) Chloride Yield Isoprene Styrene M 01 Ratio (millimol) (percent (mol) (mol) styrene/ C.) (hrs.)

isoprene Carbon tetrachloride (50) 0.504 0. 131 2. 60 10 O 18 99. 7 Ethyl chloride (50) 0. 504 0.131 2.60 10 0 18 99. G Methylene chloride (50). 0. 504 0.131 2. 60 10 0 18 59.8

was broken and the polymerization was started. The po- Example 14 lymerization continued for 65 hours at the temperature of 0 C. After the polymerization was completed, the reac- An ampoule filled Wlth Q 1111111111015 of vanadyl ch10- tion mixture was poured into 500 cc. of cold methanol. Tlde, 040504 H101 3 g.) of lsoprene, 0.139 mol (9.82 g.) The precipitated polymer at the bottom was taken out, of z'mefhylbutene-l, and 50 of ethyl Chloride W r di l d i 50 cc, f h d again poured i packed in a 100 cc. pressure bottle, and air was removed 500 cc. of methanol to be refined. After further several 35 from the bottle. Then at the reaction temperature of 0 C., Washes with methanol, the pr p was dried under the mixture was polymerized for 18 hours. The finishing rfiduced Pressure- A b 'l P l resulted- The treatments were the same as of Example 1. A rubberyleld was d i 1:at1O.WaS 910% and like polymer in an amount of 6.78 g. was obtained. The the polymer had an 1ntr1ns1c viscosity (1 of 0.175 yield was 51 1% (measured in toluene at 30 C.). The same was con- 40 firmed to be a copolymer of isoprene with isobutylcne Example 15 by infrared absorption spectrum.

Ten (10) m1ll1mols of vanadyl chloride were filled 1n Examples an arm oule in dry nitrogen current. The catalyst ampoule p All the operational conditions were id nti l a f EX- was packed in a 100 cc. pressure glass bottle together wlth ample l. 30 cc. of refined n-heptane. The bottle was then cooled to Monomer Reaction Condition Ex. No. Solvent (n- Vanadyl Yield heptane) (cc.) Isoprene Isobutylene Moi Ratio Chloride (percent) (mol) (mol) (isobutylene/ 0.) (hrs.)

isoprene) 0.101 0. 112 1.11 10 0 5s. 5 50 0. 0201 0. 244 12. 1 10 0 65 82. 5 50 0. 0101 0. 212 21. 0 10 0 65 76.6 50 0. 0020 0. 222 110. 0 10 0 65 20. 3 50 0. 244 on 10 0 05 3.9 20 0.0504 0.163 3. 24 10 +30 1 20 74.2 20 0. 0504 0. 163 3. 24 10 0 20 0s. 1 20 0. 0504 0. 103 3. 24 10 -30 20 1. 86 None 0. 0504 0. 163 3. 24 10 0 20 73. 6

Example 11 C., and thereafter added with 0.012 mol (0.65 g.) of An ampoule filled with 10 millimols of vanadyl chloride, refined butadlene a1 1d @357 mol refined 50 of ethyl Chloride Q0504 mol of isoprcne d 65 butylene. The reaction vessel Was then withdrawn from 0.163 mol of isobutylene were packed in a cc. presthe Cooling tank, and when its temperature reached 0 C-: sure bottle, eliminated of air, and polymerized at 0 C. the catalyst ampoule therein was broken to start polymfor 42 hours- The finishing treatments were the Same as erization. After 50 hours of polymerization at 0 C. under in Example 1. 7.82 g. of rubber-like polymer were 70 stirring, the resultant polymeric mixture was poured into tained. The yield was 60.9%.

Example 12 Ten (10) millimols of vanadyl chloride were filled in an ampoule in dry nitrogen current. The ampoule then methanol. The precipitated polymer was separated and washed with methanol to be refined. Upon drying the same under reduced pressure, 18.6g. of rubber-like polymer were obtained, which had an (71) of 0.125 (measured was packed in a 100 cc. pressure bottle together with 5 in toluene at 25 C.)

5 Example 16 An ampoule filled with 10 millimols of vanadyl chloride was packed in a 100 cc. pressure glass bottle together with 30 cc. of ethyl chloride. The bottle was then cooled to 70 C., thereafter 0.027 mol of refined butadiene and 0.357 mol (10 g.) of refined isobutylene were introduced thereinto under reduced pressure. When the temperature of the reaction vessel was raised to C., the catalyst ampoule was broken, and the mixture was stirred for 4 hours at that temperature. The resultant polymeric mixture was treated similarly as in Example 15. 15.3 g. of a rubber-like polymer were obtained, Which had an (1 of 0.146.

Example 17 An ampoule filled with 10 millimols of vanadyl chloride was packed in a 100 cc. pressure bottle in dry nitrogen current, together with 30 cc. of refined n-heptane and 0.214 mol of refined Z-methylbutene-l. The bottle was then cooled to 70 C., reduced of its inside pressure, introduced with 0.120 mol of refined butadiene, and Withdrawn from the cooling tank. When the temperature of the reaction vessel as a Whole rose to 0 C., the catalyst ampoule was broken to start the polymerization. After 60 hours of polymerization and finishing treatments similar to those of Example 15, g. of polymer were obtained.

Example 18 An ampoule filled with millimols of vanadyl chloride was packed in a 100 cc. pressure glass bottle together with 30 cc. of refined n-heptane and 0.091 mol of 2.5-dimethyl- 2,4-hexadiene. The bottle was cooled to 70 C., reduced of its inside pressure, and introduced with 0.228 mol. (12.8 g.) of refined isobutylene. When the temperature of the reaction vessel as a Whole reached 0 C., the catalyst ampoule was broken to start the polymerization. After 35 hours of polymerization at 0 C., the resultant polymeric mixture Was treated as in Example 15, thereby 2 g. of tacky polymer were obtained.

What is claimed is:

1. A method of preparing a solid or rubbery copolymer from a conjugated acyclic diolefin and a mono-olefin hydnocarbon having 3l2 carbon atoms which comprises copolymerizing said conjugated acyclic diolefin with said mono-olefin hydrocarbon in the presence of an inert organic solvent and a catalyst consisting of VOCl being in an amount of 0.1 to 10% based on the total weight of said conjugated acyclic diolefin, said monoolefin hydrocarbon and said inert organic solvent.

2.. A method in accordance with claim 1 wherein said catalyst consisting of VOCl is used in an amount of 0.5 to 5% based on the total weight of said conjugated diolefin, said mono-olefin hydrocarbon and said inert organic solvent.

3. Method in accordance with claim 1, wherein is-oprene is used as the conjugated diolefin.

4. Method in accordance With claim 1, wherein butadiene is used as the conjugated diolefin.

5. Method in accordance with claim 1, wherein a mixture of isoprene and butadiene is used as the conjugated diolefin.

6. Method in accordance with claim 1 wherein isobutylene is used as the monoolefin hydrocarbon.

References Cited UNITED STATES PATENTS 3,251,815 5/1966 Yamada et al. 26094.3

3,168,501 2/1965 Tocker 26085.3

2,122,826 7/1938 Peski 26085.3

2,476,000 7/ 1949 Sparks et a1 26085.3

JOSEPH L. SCHOFER, Primary Examiner.

JAMES A. SEIDLECK, Examiner.

E. J. SMITH, M. B. KURTZMAN, Assistant Examiners. 

1. A METHOD OF PREPARING A SOLID OR RUBBERY COPOLYMER FROM A CONJUGATED ACYCLIC DIOLEFIN AND A MONO-OLEFIN HYDROCARBON HAVING 3-12 CARBON ATOMS WHICH COMPRISES COPOLYMERIZING SAID CONJUGATED ACYCLIC DIOLEFIN WITH SAID MONO-OLEFIN HYDROCARBON IN THE PRESENCE OF AN INERT ORGANIC SOLVENT AND A CATALYST CONSISTING OF VOCL3 BEING IN AN AMOUNT OF 0.1 TO 10% BASED ON THE TOTAL WEIGHT OF SAID CONJUGATED ACYCLIC DIOLEFIN, SAID MONOOLEFIN HYDROCARBON AND SAID INERT ORGANIC SOLVENT. 